Fluoroaliphaticsulfonyl substituted ethylenes substituted by furyl, thenyl, or 1H-pyrrolyl groups

ABSTRACT

Fluoroaliphaticsulfonyl substituted ethylenes, useful as catalysts in polymerization of monomers, e.g., epoxide, vinyl ether, and N-vinyl monomers, are prepared by condensation of precursor fluoroaliphaticsulfonyl methanes with aldehydes or N-formyl compounds.

This is a division of application Ser. No. 455,141 filed Mar. 27, 1974,now U.S. Pat. No. 3,984,357 which application is a division ofapplication Ser. No. 300,754, filed Oct. 25, 1972, now U.S. Pat. No.3,932,526.

FIELD OF THE INVENTION

This invention relates to novel fluoroaliphaticsulfonyl substitutedethylene compounds, their use as catalysts, and to a method of theirpreparation. The invention also relates to novel precursorfluoroaliphaticsulfonyl methanes used in the method.

BACKGROUND OF THE PRIOR ART

The curing of epoxide, vinyl ether, and N-vinyl monomers in the presenceof catalysts is well known in the art. For example, epoxides can becured in the presence of boron trifluoride and complexes thereof andvinyl alkyl ethers can be polymerized in the presence of aluminumtrichloride and related Lewis acids. While the use of such acidcatalysts has been found to be advantageous in many cases, their use isoften objectionable because many acid catalysts are highly corrosive tovarious substrates, such as metals. Other catalysts are objectionablebecause of their volatility. The present invention provides catalystswhich are highly effective, substantially non-corrosive, and essentiallynon-volatile.

In one aspect, this invention provides a novel class of substitutedethylene compounds useful as catalysts for curing monomers. Theseethylenes are non-acidic, therefore non-corrosive, and they arenon-volatile during use. Some of the substituted ethylenes can be usedin admixture with the monomers to provide latently curable compositionshaving a desirably long shelf or pot life.

In another aspect, the invention provides novel precursor methanesuseful in preparing the substituted ethylenes of the invention.

Certain precursor methanes useful in the chemical reaction to obtain thenovel fluoroaliphaticsulfonyl substituted ethylenes of the invention areknown. Examples include bis(perfluoroalkylsulfonyl)methanes disclosed ina paper presented by H. A. Brown to the American Chemical Society inMinneapolis, Minn. in September 1955,bis(perfluoromethylsulfonyl)methane, disclosed in U.S. Pat. No.2,732,398 and by Gramstad and Haszeldine in Journal of Chemical Soc.4069 (1957), and bis(perfluoroalkylsulfonyl)methanes, disclosed in U.S.Pat. No. 3,281,472. Likewise, somewhat related substituted ethylenes areknown, e.g., bis(alkylsulfonyl) ethylenes and perfluoromethyl sulfonylethylenes see U.S. Pat. No. 3,335,188 and L. M. Yagupolski and A. G.Pateleimonov in Zh. Obshch. Khim., 36, (3) 416 (1966), respectively, butthese substituted ethylenes are considerably weaker than the substitutedethylenes of the invention, if at all effective, in catalyzing epoxide,vinyl ether, and N-vinyl monomer polymerization.

DESCRIPTION OF THE INVENTION

The novel fluoroaliphaticsulfonyl substituted ethylenes of the inventionare formed by the chemical condensation of certain precursorfluoroaliphaticsulfonyl methanes with aldehydes or N-formyl compounds,i.e., compounds characterized by containing a "--CHO" group. Thefluoroaliphatic sulfonyl substituted ethylenes of the invention arepreferably represented by the general formula: ##STR1## wherein R_(f) isa monovalent saturated fluoroaliphatic radical, for example, containingfrom 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms) with themajority of the carbon atoms preferably being perfluorinated; X is amonovalent, non-ionic, election-withdrawing radical that is at least aselectron-withdrawing as a benzoyl radical [i.e., having a Hammett sigma(para) value of at least 0.5], e.g., a cyano, arylcarbonyl,alkylcarbonyl, perfluoroalkylcarbonyl, arylsulfonyl,perfluoroalkylsulfonyl, nitro, fluorosulfonyl, or chlorosulfonyl group,(preferably X has the general formula R'_(f) SO₂ where R'_(f) is afluoroaliphatic group as defined for R_(f) above, including R'_(f) beingidentical to R_(f)); R is hydrogen, alkyl (preferably having 1-3 carbonatoms), or phenyl; R' is the same as R with at least one of R or R'being hydrogen; n is an integer from zero to 7 depending on Z; n is 1 to7 when Z is hydrogen, alkyl, alkenyl, aryl, arylalkyl, alkylaryl or2-furyl; n is zero when Z is aryl or arylmethyl (e.g., benzyl) or amino,dialkylamino, arylalkylamino, diarylamino, alkylamino, arylamino orheterocyclic nitrogen-containing organic radical having a free valenceon a ring between nitrogen atom (e.g., a morpholino group) or Z is anunsaturated, conjugated heterocyclic organic radical containing one ormore oxygen, sulfur, or nitrogen heteroatom and having a free valence ona carbon atom (e.g., ##STR2## Additionally, Z may contain 1-3substituent groups which can vary widely from highly electron-donatinggroups to highly electron-withdrawing groups, provided they are lessreactive than the formyl group with the precursor methane. Exemplarysubstituents include groups such as halo (e.g., chloro, bromo, fluoro),cyano, hydroxy, nitro, lower alkyl (1-3 carbon atoms), lowerperfluoroalkyl (1--3 carbon atoms), alkylcarbonyl, arylcarbonyl,alkoxycarbonyl, lower alkenyl, alkylsulfonyl, fluorosulfonyl, alkoxy,etc.

As mentioned above a majority of the carbon atoms of the fluoroaliphaticgroups R_(f) and R'_(f) are perfluorinated. The term "perfluorinated"and the prefex "perfluoro" is employed to denote substitution of allcarbon-bonded hydrogen atoms by fluorine atoms, in accord with therecognized usage of these terms, see U.S. Pat. No. 2,732,398. This usagecarries no implication of similarities in properties betweencorresponding groups and compounds of hydrocarbon and fluorocarbonsystems; hydrogen and fluorine are not chemically equivalent or similar.

The above-mentioned fluoroaliphatic groups can contain chlorine atomsbonded to the carbon atoms as well as having fluorine and hydrogen atomsbonded to carbon atom. Preferably for any two carbons bonded together ina chain, there is no more than one hydrogen atom or one chlorine atom,with fluorine atoms occupying the remaining non-skeletal carbon bonds.

The fluoroaliphatic radical may be a straight or branched chain, or astraight chain including a cyclic portion. Additionally, thefluoroaliphatic group may contain an oxygen atom linking two carbonatoms, e.g., --CF₂ OCF₂ --, or a nitrogen atom linking three carbonatoms, e.g., (R_(f) CF₂) NCF₂ --. Exemplary fluoroaliphatic groupsinclude perfluoromethyl, perfluorobutyl, perfluorooctyl,perfluorododecyl, perfluoroisopropyl, perfluoro(2-cyclohexylethyl),omega-chloroperfluorohexyl, 2-hydroperfluoropropyl,perfluoro(3-morpholinopropyl), and perfluoro(3-piperidinopropyl).

The combined electron withdrawing nature of the SO₂ R_(f) group and theX group is influential in providing the desired catalytic activity; thegreater the electron withdrawing nature, the greater the catalyticactivity will be of the fluoroaliphaticsulfonyl substituted ethylenecompounds of the invention. The electron withdrawing nature of the SO₂R_(f) and X groups can be determined by various known methods, e.g., byHammett sigma (para) values as obtained by the method disclosed by H. H.Jaffe, Chem. Rev. 53, 191 (1953). For the purpose of providing usefulcatalytic activity the combined electron withdrawing nature of the SO₂R_(f) and X groups should provide a sigma (para) value of at least 1.0,with the X group having a sigma (para) value of at least 0.5.Preferably, the SO₂ R_(f) group has a sigma (para) value of at least0.7, providing a combined sigma (para) value of at least 1.2 for the twogroups. A benzoyl radical, for example, has a sigma (para) value of 0.5.A preferred SO₂ R_(f) group is SO₂ CF₃ having a sigma (para) value of0.9. A very useful fluoroaliphaticsulfonyl substituted ethylene isprovided when both X and and SO₂ R_(f) are SO₂ CF₃ groups. Additionally,exemplary organic radicals providing useful X groups include cyano,arylcarbonyl, alkylcarbonyl, perfluoroalkylcarbonyl,perfluoroalkylsulfonyl, nitro, fluorosulfonyl, and chlorosulfonylgroups.

The novel substituted ethylene compounds of the invention are mostconveniently formed by condensation of precursor fluoroaliphaticsulfonylmethanes with aldehydes and N-formyl compounds in a chemicalcondensation reaction which can be illustrated as follows: ##STR3##wherein X, R_(f), Z, R and R' are as defined above. The reaction of theN-formyl compounds is usually in the presence of a carboxylic acidanhydride such as acetic anhydride and propionic anhydride.

In another method, the substituted ethylene compounds can be obtained bythe reaction of an alkali metal salt of the fluoroaliphaticsulfonylmethane with the N-formyl compound in presence of an active acid halidewhich reaction can be illustrated as follows: ##STR4## wherein Q₁ and Q₂can be monovalent radicals such as hydrogen, alkyl, aryl, arylalkyl or(when taken together) a divalent radical such as --(CH₂)₅ -- or --CH₂CH₂ OCH₂ CH₂ -- to form a ring structure. The active acid halides usefulin the process are those that form complex halides with the N-formylcompounds, such as are described, for example, by H. Eilingsfeld, etal., Angew, Chem., 72 836 (1960). Examples of active acid halidesinclude benzoyl chloride, benzoyl bromide, acetyl chloride, phosphorusoxychloride, phosphorus trichloride, thionyl chloride and phosgene. Inthe reaction, an equimolar amount of the active acid chloride is usuallyused.

Yet another useful method of obtaining certain of the substitutedethylene compounds of the invention includes condensation of activehydrogen-containing substituted ethylene compounds (previously madeaccording to the invention), e.g., (CF₃ SO₂)₂ C═CHCH₂ C₆ H₅, withadditional aldehyde to provide substituted ethylene compounds havingadditional substituents.

Useful fluoroaliphatic sulfonyl methanes are preferably represented bythe general formula X--CH₂ --SO₂ R_(f) wherein R_(f) and X are asdescribed above. Certain known compounds will provide usefulfluoroaliphatic methane precursors, e.g., see the aforementioned articleby T. Gramstad and R. N. Haszeldine. Known compounds such as CF₃ SO₂ CH₂SO₂ CF₃ and CF₃ SO₂ CH₂ SO₂ C₆ H₅ provide useful examples.

It will be noted that the combined electron-withdrawing nature of theSO₂ R_(f) and the X groups will be sufficient to at least make one ofthe hydrogen atoms of the methylene group of the fluoroaliphaticsulfonylmethane precursor sufficiently acidic, i.e., having a pKa of less than7, to permit the condensation reaction with an aldehyde or N-formylcompound to occur, and to provide compounds of the invention havingcatalytic utility.

Novel fluoroaliphaticsulfonyl methane precursors have been prepared andfound useful in providing the novel substituted ethylenes of theinvention on condensation with an aldehyde or an N-formyl compound.These precursors are preferably represented by the general formula:##STR5## wherein R_(f) is as described above and R₃ is alkyl, forexample having 1 to 18 carbon atoms (preferably 1 to 8), afluoroaliphatic group such as R_(f) as defined above, or aryl such as aphenyl, naphthyl, biphenylyl, tolyl, or anisyl group.

The novel fluoroaliphaticsulfonyl methanes of the invention areconveniently prepared by reaction of a fluorogliphaticsulfonyl methylmagnesium halide with a suitable acyl halide as is preferablyrepresented by the following general formula: ##STR6## wherein X" ismonovalent chlorine, bromine or iodine, X' is monovalent chlorine orfluorine, and R_(f) and R₃ are as defined above.

The reaction for producing the novel fluoroaliphaticsulfonyl methanes ismost conveniently carried out by mixing the acyl halide in an inertorganic reaction medium such as tetrahydrofuran containing thefluoroaliphatic methyl magnesium halide under anhydrous conditions,acidifying the mixture, and removing the product from the organicreaction medium.

It should be noted that the novel fluoroaliphaticsulfonyl methanes, aswell as providing precursors for the fluoroaliphatic substitutedethylenes of the invention, are themselves useful acidic catalysts forepoxy polymerization.

The aldehydes and N-formyl compounds useful in the condensation reactionto produce the novel fluoroaliphaticsulfonyl substituted ethylenes ofthe invention can be represented by the general formula Z(CR═CR')_(n)CHO wherein R, R', Z, and n are as defined above. Exemplary usefulaldehydes and N-formyl compounds include:

AROMATIC ALDEHYDES

benzaldehyde

4-nitrobenzaldehyde

2-chlorobenzaldehyde

4-bromobenzaldehyde

4-cyanobenzaldehyde

4-hydroxybenzaldehyde

3,4-dichlorobenzaldehyde

2-hydroxybenzaldehyde

3,4-dihydroxybenzaldehyde

3-bromo-6-methoxybenzaldehyde

4-methoxybenzaldehyde

mesitaldehyde

4-hydroxy-3-ethoxybenzaldehyde

3-bromo-6-hydroxybenzaldehyde

2,3-dimethoxy-5-bromobenzaldehyde

2,5-dimethoxybenzaldehyde

2-isopropoxybenzaldehyde

2,4,5-trimethoxybenzaldehyde

4-valeryloxybenzaldehyde

3-methyl-4-benzyloxybenzaldehyde

3,5-di-t-butyl-4-hydroxybenzaldehyde

4-acetoxybenzaldehyde

4-acetamidobenzaldehyde

4-(methoxymethyl)benzaldehyde

3,4,5-triacetoxybenzaldehyde

2-benzaldehydesulfonic acid, sodium salt

4-methoxybenzaldehyde-3-sulfonic acid, sodium salt

4-fluorobenzaldehyde

3-trifluoromethylbenzaldehyde

4-formylphenoxyacetic acid, sodium salt

terephthalaldehyde

4-hydroxyisophthalaldehyde

4 methoxyisophthalaldehyde

2,5-dimethoxyterephthalaldehyde

1-naphthaldehyde

2-naphthaldehyde

azulene-1-carboxaldehyde

2-hydroxy-1-naphthaldehyde

ferrocene carboxaldehyde

5,6,7,8-tetrahydronaphthalene-2-carboxaldehyde

9-anthraldehyde

2,5-dibutoxyterephthaladehyde

2,4-dimethyl-7-isopropylazulene-1-carboxaldehyde

tolualdehyde

4-(2'-chloroethylthio)benzaldehyde

HETEROCYCLIC ALDEHYDES

2-furaldehyde

thiophene-2-carboxaldehyde

pyridine-2-carboxaldehyde

pyrrole-2-carboxaldehyde

β-(2-thienyl)acrolein

3,4-dimethylpyrrole-2-carboxaldehyde

4-carbethoxy-5-methyl-2-furaldehyde

4-carbethoxy-5-phenyl-2-furaldehyde

3,5-dimethyl-4-acetylpyrrole-2-carboxaldehyde

ARYLALKYL OR ARYLALKENYL ALDEHYDES

phenylacetaldehyde

cinnamaldehyde

11-phenylundecapentaenal

ACYCLIC ALDEHYDES

crotonaldehyde

acrolein

acetaldehyde

n-butyraldehyde

N-FORMYL COMPOUNDS

formamide

N-benzylformamide

N-(p-methoxy benzyl)formamide

N-triphenylmethylformamide

4-formylaminotoluene

1-formylaminonaphththalene

5-formylaminocaproamide

N-formylmorpholine

dimethyl formamide

formanilide

A list of other useful aldehydes can be found in Chap. 2, OrganicReactions, Vol. 15, (1967) edited by A. C. Cope, New York.

One convenient method for preparing the fluoroaliphaticsulfonylsubstituted ethylene compounds of this invention consists in bringing afluoroaliphaticsulfonyl methane precursor into intimate contact with analdehyde in a liquid reaction medium, which is non-reactive to thereactants and the product, at a suitable temperature which is generallyin the range of 60° to 150° C., and maintaining the mixture at thetemperature until the reaction is essentially complete. The liquidreaction medium is preferably a solvent for the reactants and theproduct; most preferably it will also form an azeotrope with water thatis a reaction byproduct, giving a convenient means of removing the waterfrom the reaction mixture. Examples of suitable reaction media includebenzene, toluene, xylene, mesitylene, and chloroform. Anhydrous basictertiary amines such as pyridine can also be used as a reaction mediumalthough they usually produce low yields of the condensationproduct--especially with bis(fluoroaliphaticsulfonyl)methanes. Stronglybasic solutions such as aqueous sodium hydroxide or sodium methoxide areto be avoided because they may degrade the condensation product. Uponcompletion of the reaction (which is evidenced by cessation of theproduction of water), the condensation product is separated from thereaction mixture, e.g., by distillation or evaporation of reactionmedium, with further purification, if desired, by re-crystallizationfrom liquid anhydrous media.

The preferred reaction temperature range is from about 60° C. to about150° C. but temperatures as low as 25° C. and as high as 165° C. or evenhigher can be used.

The reaction, to proceed satisfactorily, may require the presence of acatalytic amount of organic base such as piperidine, triethylamine, orthe organic acid salt of piperidine or triethylamine. Use of a catalyst,however, is not required where the precursor fluoroaliphaticsulfonylmethane is a bis(perfluoroaliphaticsulfonyl) methane.

For convenience, the reactions of this invention are conducted at normalatmospheric pressure but pressures above and below atmospheric pressurecan be used. The reactor can be a vessel of simple design constructed ofany non-reactive materials such as glass, ceramic ware, or stainlesssteel and is preferably provided with means for agitation, cooling andheating, and equipped to protect the charge from atmosphericcontaminants.

The molar ratio of the precursor fluoroaliphaticsulfonyl meethane to thealdehyde used in the method may be varied, but best results are obtainedwhen equimolar amounts of aldehyde and fluoroaliphaticsulfonyl methaneare used. With aliphatic aldehydes such as acetaldehyde, however, amolar ratio of 2:1 or greater (aldehyde to methane) is preferred.

The particular amount of fluoroaliphaticsulfonyl ethylene catalyst to beused and the temperature of polymerization are dependent on theparticular monomers and catalyst used, as well as the particularapplication to be made. Generally, the amount of fluoroaliphaticsulfonylsubstituted ethylene catalyst to be used will be in the range of 0.1 to20 weight percent, preferably 0.1 to 5 weight percent based on theweight of monomeric material. The temperature will generally be 25°-150°C. or higher.

The vinyl monomers polymerized by fluoroaliphaticsulfonyl substitutedethylenes of the invention contain a vinyl group and are typified byvinyl alkyl ethers, such as vinyl methyl ether, vinyl ethyl ether, vinyln-butyl ether, vinyl 2-chloroethyl ether, vinyl isobutyl ether, vinylphenyl ether and vinyl 2-ethylhexyl ether, vinyl ethers of substitutedaliphatic alcohols, such as ω-hydroxybutyl vinyl ether, and N-vinylcompounds such as N-vinyl-N-methyl octanesulfonamide. A description ofvinyl monomers and their use in preparing polymers is set forth in"Vinyl and Related Polymers", by Schildknecht, published by John Wiley &Sons, Inc., New York (1952).

The epoxide monomers polymerized by the fluoroaliphaticsulfonylsubstituted ethylenes of the invention include both monomeric andpolymeric aliphatic, cycloaliphatic, aromatic or heterocyclic epoxycompounds typically having an epoxy equivalency (i.e., the number ofepoxy groups contained in the average molecule) of from 1.0 to 6.0,preferably 1 to 3, this value being the average molecular weight of theepoxide divided by the epoxide equivalent weight. The epoxide monomersare well known and include such epoxides as epihalohydrins, e.g.,epichlorohydrin, alkylene oxides, e.g., propylene oxide, styrene oxide,alkenyl oxides, e.g., butadiene oxide, glycidyl esters, e.g., glycidylacetate, glycidyl-type epoxy resins, e.g., the diglycidyl ethers ofBisphenol A and of novolak resins, such as described in "Handbook ofEpoxy Resins", by Lee and Neville, McGraw-Hill Book Co., New York(1967).

Particularly useful epoxides which can be used in this invention arethose which contain one or more cyclohexane oxide groups such as theepoxycyclohexanecarboxylates, typified by3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate,3,4-epoxy-2-methylcyclohexane carboxylate, andbis(3,4-epoxy-6-methylcyclohexylmethyl)adipate. For a more detailed listof useful epoxides of this nature, reference is made to the U.S. Pat.No. 3,117,099.

Further epoxides which are particularly useful in the practice of thisinvention include glycidyl ether monomers of the formula ##STR7## whereR is alkyl or aryl and n is an integer of 1 to 6. An example is theglycidyl ethers of polyhydric phenols obtained by reacting a polyhydricphenol with an excess of chlorohydrin, such as epichlorohydrin, e.g.,the diglycidyl ether of bisphenol A. Further examples of epoxides ofthis type which can be used in the practice of this invention aredescribed in U.S. Pat. No. 3,018,262.

In particular, epoxides which are readily available include propyleneoxide, epichlorohydrin, styrene oxide, vinyl cyclohexane oxide,glycidol, glycidyl methacrylate, diglycidyl ether of bisphenol A (e.g.,Epon 828 and DER 332), vinylcyclohexene dioxide (e.g., ERL-4206),3,4-epoxycyclohexylmethyl3,4-epoxycyclohexane carboxylate (e.g., ERL4221), 3,4-epoxy-6-methycyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate (e.g., ERL-4201),bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate (e.g., ERL 4289),bis(2,3-epoxycyclopentyl)ether (e.g., ERLA-0400), aliphatic epoxymodified with polypropylene glycol (e.g., ERL-4050 and ERL-4052),dipentene dioxide (e.g., ERL-4269), epoxidized polybutadiene (e.g.,Oxiron 2001), 1,4-butanediol diglycidyl ether (e.g., Araldite RD-2),polyglycidyl ether of phenolformaldehyde novolak (e.g., DEN-431 andDEN-438) and resorcinol diglycidyl ether (e.g., Kopoxite).

EXAMPLES

This invention is further illustrated by the following examples whereinall parts are given by weight and temperatures are in degrees centigradeunless otherwise specified.

EXAMPLE 1 Catalyst Preparation

A mixture of 7.5 g. (0.05 mole) of 1-naphthaldehyde, 14.0 g. (0.05 mole)of bis(perfluoromethylsulfonyl)methane and 50 ml. of benzene was heatedunder reflux (4 hrs.) until water ceased to be formed. During reaction,the water was removed by distillation using a Barrett-typewater-receiver. The mixture was heated under reduced pressure (0.02 mm)to 100° C. leaving a residue which was recrystallized from hexane toyield 12.7 g. of the fluoroaliphaticsulfonyl substituted ethylenecompound, 1,1-bis(perfluoromethylsulfonyl)-2-(1'-napthyl)ethylene,having a melting point of 91-93°, and a chemical structure as follows:##STR8##

Epoxide Polymerization

A solution of 0.03 g. of the1,1-bis(perfluoromethylsulfonyl)-2-(1'-naphthyl)ethylene prepared abovein 0.3 ml. of methylene chloride was added with stirring to 3.5 g. of3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate containing0.1% of H₂ O. The mixture was exposed to air for 15 min. and then heatedat 75° for 5 min. giving a hard cured polymer.

EXAMPLE 2

A mixture of 8.0 g. (0.08 mole) of benzaldehyde, 14.0 g. (0.05 mole) ofbis(perfluoromethylsulfonyl)methane, 0.1 g. of piperidine and 50 ml. ofbenzene was refluxed until production of water ceased. Benzene, waterand starting material were removed by heating, giving 15 g. of a solidresidue. Recrystallization of the solid residue from hexane gave 13.3 g.of β,β-bis(perfluoromethylsulfonyl) styrene, (CF₃ SO₂)₂ C═CHC₆ H₅, m.p.39°-41°.

EXAMPLE 3

A 250 ml. dry flask fitted with a stirrer, addition funnel and condenserconnected to a drying tube was charged with 28 g. (0.1 mole) ofbis(perfluoromethylsulfonyl)methane and 75 ml. of dry tetrahydrofuran.To the stirred solution was added 58 ml. of 3.0 molar methylmagnesiumchloride in tetrahydrofuran. The mixture was stirred at room temperaturefor 0.5 hrs. and 15.0 g. (0.15 mole) of benzaldehyde added. Theresultant mixture was stirred at room temperature for 3.5 hrs. andhydrolyzed by the slow addition of 80 ml. of 3N HCl. The organic phasewas separated and heated to remove tetrahydrofuran and the residueextracted with diethyl ether. The extract was dried over magnesiumsulfate and distilled to yield 13.3 g. of (CF₃ SO₂)₂ C═CHC₆ H₅, b.p.103°-104° (0.05 mm.), which solidified on standing.

Polymerization of vinylcyclohexene dioxide to a solid cured product waseffected at room temperature using about 1% by weight of the abovebenzaldehyde condensation product dissolved in methylene chloride.

EXAMPLE 4

A mixture of 10.0 g. (0.08 mole) of phenylacetaldehyde, 28.0 g. (0.1mole) of bis(perfluoromethylsulfonyl)methane and 80 ml. of benzene wasstirred under reflux and water (1.3 ml.) continuously removed. Thereaction yielded 12.5 g. of1,1-bis(perfluoromethylsulfonyl)-3-phenylpropene, (CF₃ SO₂)₂ C═CHCH₂ C₆H₅, b.p. 112° (0.01 mm.).

EXAMPLE 5

A mixture of 4.8 g. (0.05 mole) of 2-furaldehyde, 14.0 g. (0.05 mole) ofbis(perfluoromethylsulfonyl)methane and 50 ml. of benzene was stirredunder reflux and water continuously removed. The reaction yielded 11.8g. of 1,1-bis(perfluoromethylsulfonyl)2-(2'-furyl)ethylene, ##STR9##b.p. 109°-110° (0.01 mm). The condensation product was crystallized fromhexane, giving a product having a m.p. of 78°-79°.

EXAMPLE 6

Using procedures described in Example 2,β,β-bis-(perfluoromethylsulfonyl)-o-chlorostyrene, b.p. 117° at 1 mm.,was prepared by condensation of o-chlorobenzaldehyde andbis(perfluoromethylsulfonyl)methane.

EXAMPLE 7

Using procedures described in Example 2,β,β-bis(perfluoromethylsulfonyl)-p-nitrostyrene, m.p. 102°-104°, wasprepared by condensation of p-nitrobenzaldehyde withbis(perfluoromethylsulfonyl)methane.

EXAMPLE 8

Using procedures described in Example 1,β,β-bis(perfluoromelthylsulfonyl)-3-ethoxy-4-hydroxystyrene, m.p.82°-84°, was prepared by condensation of 3-ethoxy-4-hydroxybenzaldehydewith bis(perfluoromethylsulfonyl)methane. The compound wasrecrystallized from hexane.

EXAMPLE 9

A mixture of 5.0 g. (0.005 mole) of (C₈ F₁₇ SO₂)₂ CH₂, 1.6 g. (0.01mole) of 1-naphthaldehyde and 100 ml. of mesitylene was heated underreflux for 9 hrs. until water ceased to be produced. The mixture wasallowed to cool and then filtered giving 5.1 g. of crude product.Recrystallization of the crude product from hexane gave 2.6 g. of thefollowing product. m.p. 113°-114°. ##STR10##

Anal. Calcd: C,30.1; F,57.8; H,0.7. Found: C,30.1; F,57.0; H,0.8.

EXAMPLE 10

A mixture of 14 g. (0.05 mole) of bis(perfluoromethylsulfonyl)methane,6.6 g. (0.05 mole) of cinnamaldehyde and 50 ml. of benzene was heatedunder reflux until evolution of water ceased. There was obtained about7.3 g. of ##STR11##

EXAMPLE 11

Using the procedure described in Example 10, the reaction ofbis(perfluoromethylsulfonyl)methane and pyrrole-2-carboxaldehyde gave##STR12##

EXAMPLE 12

Crotonaldehyde (3.5 g.; 0.05 mole) was added to 14 g. (0.05 mole) ofbis(perfluoromethylsulfonyl)methane dissolved in 50 ml. of benzene. Themixture was heated under reflux until water evolution ceased. Thereaction yielded (CF₃ SO₂)₂ C═CHCH═CHCH₃, b.p. 78° (0.2 mm.) and ahigher boiling sulfone product having 31.7% fluorine and a molecularweight of about 1120.

EXAMPLE 13

Acetaldehyde (9.3 g.; 0.21 mole) in 20 mol. of benzene was added to 28g. (0.1 mole) of bis(perfluoromethylsulfonyl)methane in 50 ml. ofbenzene. The mixture was stirred at room temperature for one hour andheated then under reflux until evolution of water ceased. The reactionyielded 8 g. of (CF₃ SO₂)₂ C═CHCH═CHCH₃, b.p. 108°-112° (2 mm.).

EXAMPLE 14

The reagent CF₃ SO₂ CH₂ MgCl was prepared from 22.0 g. (0.15 mole) ofmethyl perfluoromethylsulfone and 0.2 mole of methylmagnesium chloridein tetrahydrofuran. Butyryl chloride (30.0 g.; 0.3 mole) was added atroom temperature and the mixture stirred for two hours. The mixture washydrolyzed with 3 N HCl, the tetrahydrofuran phase separated and heatedto remove solvent. The residue was dissolved in diethyl ether and thesolution (dried over MgSO₄) heated to remove the ether, giving 14 g. ofthe novel fluoroalkylsulfonyl methane precursor, CF₃ SO₂ CH₂ COC₃ H₇b.p. 90° C. (5 mm.). A sample was recrystallized from water, m.p.67.5°-68.5° C.

Anal. Calcd: C, 33.0; F, 26.1; H, 4.1. Found: C, 33.1; F, 25.8; H, 4.5.

EXAMPLE 15

Using procedures described in Example 14, the novel fluoroalkylsulfonylmethane precursor, C₄ F₉ SO₂ CH₂ COC₆ H₅, was prepared from methylperfluorobutyl sulfone and benzoyl chloride. The compound melted at73°-75° C.

EXAMPLE 16

Using procedures described in Example 14, 22.0 g. (0.15 mole) of methylperfluoromethylsulfone was converted to CF₃ SO₂ CH₂ MgX and to this wasadded perfluoroacetyl chloride (0.22 mole), giving 20.7 g. liquid, b.p.85°-88° (150 mm.) which contained the novel fluoroalkylsulfonyl methaneprecursor CF₃ SO₂ CH₂ COCF₃, and its enol isomer.

EXAMPLE 17

Dimethylformamide (23.4 g; 0.32 mole) was slowly added to a stirredmixture of 100 g (0.32 mole) of (CF₃ SO₂)₂ CHK, 48 g. (0.34 mole) ofbenzoyl chloride and 350 ml. of carbon tetrachloride under nitrogen(slight exotherm). The mixture was stirred at room temperature for onehour and then at 60° C. for one hour. After addition of 250 ml. ofcarbon tetrachloride, filtration yielded about 135 g. of crude productcontaining potassium chloride. Recrystallization from toluene gave 75 g.of 1,1-bis(perfluoromethylsulfonyl)-2-dimethylaminoethylene, (CF₃ SO₂)₂C═CHN(CH₃)₂, m.p. 116°-118° C.

Anal. Calcd: C, 21.3; F, 34.0; N, 4.2. Found: C, 21.4; F, 34.3; N, 4.1.

A mixture of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylateand the above product (2% by weight) was heated at 150° C. for 15 hoursgiving a hard polymer.

EXAMPLE 18

Formamide (2.8 g.; 0.06 mole) was slowly added to a stirred mixture of20.0 g. (0.06 mole) of (CF₃ SO₂)₂ CHK, 9.8 g. (0.07 mole) of benzoylchloride and 75 ml. of carbon tetrachloride. The mixture was heatedunder reflux for 1.5 hours. Filtration gave 20.7 g. of crude productwhich was slurried with diethyl ether to remove KCl, leaving about 19 g.of ether soluble (CF₃ SO₂)₂ C═CHNH₂ (m.p., 121°-122° from chloroform).

Anal. Calcd: C, 15.6; F, 37.1; H, 1.0. Found: C, 15.8; F, 37.2; H, 1.2.

EXAMPLE 19

Using procedures found in Example 17, the reaction of N-formylmorpholinewith the potassium salt of bis(perfluoromethylsulfonyl)methane gave##STR13##

The reaction of bis(perfluoromethylsulfonyl)methane and N-formylcompounds was also carried out using solvents such as acetic anhydride,but the yields of the product were lower.

EXAMPLES 20-28

The following compounds are further Examples prepared by theabove-described procedures:

    CH.sub.3 CH═C(CH.sub.3)CH═C(SO.sub.2 CF.sub.3).sub.2

    c.sub.6 h.sub.5 ch═c(ch.sub.3)ch═c(so.sub.2 cf.sub.3).sub.2 ##STR14##

    ch.sub.3 c(ch.sub.3)═chch.sub.2 ch.sub.2 c(ch.sub.3)═chch═c(so.sub.2 cf.sub.3).sub.2

    (c.sub.6 h.sub.5).sub.2 c═chch═c(so.sub.2 cf.sub.3).sub.2

what is claimed is:
 1. A fluoroaliphaticsulfonyl ethylene compoundespecially suited as a catalyst in epoxide, vinyl ether, and N-vinylmonomer polymerization and having the formulawherein R_(f) ismonovalent, saturated fluoroalkyl radical having from 1 to 18 carbonatoms; X is a monovalent, nonionic, electron withdrawing radical atleast as electron withdrawing as a benzoyl radical selected from thegroup consisting of a cyano, phenylcarbonyl, alkylcarbonyl,perfluoroalkylcarbonyl of 2 to 18 carbon atoms, phenylsulfonyl,perfluoroalkylsulfonyl of 1-18 carbon atoms, nitro, fluorosulfonyl, orchlorosulfonyl group; R is hydrogen, an alkyl group, or a phenyl group;R' is the same as R with at least one being hydrogen; n is an integerfrom 0 to 7 depending on Z; n is 1 to 7 when Z is 2-furyl; n is zerowhen Z is a monovalent unsaturated, conjugated heterocyclic organicradical selected from the group consisting of furyl, thenyl and1H-pyrrolyl.
 2. The compound of claim 1 wherein X is SO₂ R'_(f) whereinR'_(f) is perfluoroalkyl of 1-18 carbons.
 3. The compound of claim 2wherein R'_(f) and R_(f) are perfluoromethyl groups.
 4. ##STR16## 5.##STR17##